Manufacture of liquid hydrocarbons



preferably under pressure and in the pres- Penman 11, m2

I UNITED STATES PATENT OFFICE m ISRAEL WATEBIAN, OI DELIT, NETHERLANDS, ASSIGNOB '10 DE BATAAIBGEB PETROLEUM IAATSGHAIPPH, 01" THE HAGUE, NETHERLANDS MANUFACTURE OI LIQUID EYDBOGARBONS Io Drawing. Application filed March 13, 1929, Serial No. 846,818, and in the Nether-land: April 18,- 1928.

This invention concerns a process for the manufacture of liquid roducts from coal or carbonaceous materials, and for the liquefaction of these materials.

It is known that coal or other materials rich in carbon, such as coaltar, coaltar pitch, mineral oils, products and residues from the distillation of mineral oils, etc. can be partly converted into liquid products by heating,

ence of hydrogen or substances which yield hydrogen under the conditions of the reaction and in the presence of'certain substances as contact masses or catalysts.

Generally speaking thismethod has the disadvantage that the yield of the required reaction products, for instance kerosene and benzine, cannot be sufiiciently controlled. In addition to these products there are formed on the one hand gaseous compounds which gaseous and asphaltic by-products being reare of much less value and, moreover, are technically diflicult to recover, and on the other hand asphaltic roducts which likewise unfavourably in uence the economic effect of the process.

According to the present invention this drawback is for the greaterpart eliminated, and a high yield can be obtained of valuable liquid reaction products, the quantities of duced to a minimum.

The principle of the invention consists in performing the reaction in at least two stages, in the first of which the pressure, temperature and hydrogen concentration are so regulated that few aseous or low-boiling reaction products are ormed, while in the second stage the conditions of reaction are altered in such a way that, mainly, only the required reaction product is formed, i. e. benzine or kerosene.

As a rule the first stage of the reaction is carried out at relatively low temperatures. In this way the formation of large quantities of low-boiling cracking products, such as benzine, which may cause flocculence and, in consequence, a deposition of cokes, is avoided. After the first stage the more volatile compounds formed can, if necessary after partial cooling, be run OH and condensed. It

is preferable, however, to run off the gaseous products formed at the end of the first or of each stage, while still maintaining a high temperature, which has been found to have a favourable influence upon'the yield of the desired liquid reaction products. After this the material is heated again and compressed with hydrogen, the temperature being kept higher or gradually raised higher than in the first stage. In this manner a maximum yield is obtained of valuable liq Bid reaction products, i. e. benzine or kero-- sene. I

The conditions under which the two stages of the reaction are carried out may be varied in difi'erent ways; for instance, in both stages the temperature may be about the same, the pressure in the first stage then being kept lower; also, by means of the hydrogen concentration the process can be regulated so that in the first stage a minimum quantity of gaseous and low-boiling products is produced.

It is known that several substances can be used as catalysts or contact masses for the liquefaction of coal or other carbonaceous materials.

According to the present invention the benzine and kerosene yields can be improved by using as the catalysts or contact masses in one or both of the stages of the reaction, molybdenum or molybdenum compounds or materials containing molybdenum or molybdenum compounds, together with iodine or iodine'comp'ounds or materials containing iodine or iodine compounds. Accordingly, the expressions molybdenum-containing contact mass and iodine-containing contact mass are intended to cover any of the respective substances or materials specified,

Furthermore, experiments have shown that it may be of advantage to use in the first stage a catalyst which promotes liquefaction, While in the second stage a catalyst is used which promotes the'formation of the reaction products required.

Particularly favourable results have been obtained by this invention by adding in the first stage molybdenum or molybdenum compounds of materials containmg molybdenum or molybdenum compounds, together with iodine or iodine compounds or materi als containing iodine or iodine compounds.

Example 203 grammes. of ground Carisborg briquettes, containing 181.5 grammes of dry ash-free carbon, are heated in two stages 1n an autoclave with, hydrogen and a few grammes of molybdic acid anhydride (M00 In the first stage the initial pressure is 100 kilos/g nf; the temperature is raised to about 425 C. and afterwards gradually raised to 460 C. Thereafter the gaseous products are run off while still at a high temperature and, after the additlon of a small quantity of iodine, the compression is repeated with hydrogen and the temperature raised to about 490 C., at which temperature the mass is kept for a time. The yield of liquid reaction products is about calculated on the dry and ash-free coal,

. for the greater part consisting of benzine and kerosene.

What I claim is: 1. A process for the roduction of liquid hydrocarbons from car onaceous materials, which comprises heating carbonaceous material under elevated pressure in the presence of hydrogen and of a molybdenumand iodine-containing contact mass at elevated temperature in a manner to avoid as much as possible an intensive splitting and consequent formation of hydrocalbons oflow molecular weight; withdrawing the lower-boiling reaction products in a gaseous state from the reaction vessel to separate them from the high-boiling residue, while the reaction mass is still at high temperature; and again heating the high-boiling residue under the pressure in the presence of hydrogen and of a molybdenumand iodine-containing contact mass for converting the residue into lowerboiling hydrocarbons.

2. A process for the production of liquid hydrocarbons from carbonaceous materials, which comprises heating carbonaceous material under elevated pressure in the presence of hydrogen and of a molybdenumand iodine-containing contact mass at elevated temperature to avoidv as much as possible an intensive splitting and consequent formation of hydrocarbons of low molecular weight; Withdrawing the lower-boiling reaction products in a gaseous state from the reaction vessel to separate them from the high-boiling residue, while the reaction mass is still at high temperature; again heating the highboiling residue under pressure in the presence of hydrogen and of a molybdenumand iodine-containing contact mass for converting the residue into lower-boiling hydrocarbons; separating the lower-boiling reaction products obtained in the second heating treatment from the high-boiling residue by withdrawing said reaction products in a gaseous state from the reaction vessel, while the reaction mass is still at high temperature; and then heating said high-boiling residue under pressure in the presence of hydrogen and of a molybdenumand iodine-containing contact mass to convert the residue into lowerboiling hydrocarbons.

3. A process for the production of liquid hydrocarbons from carbonaceous .materials, which comprises heating carbonaceous mate rial under elevated pressure in the presence ofhydrogen and of a molybdenum-containing mass at elevated temperature to avoid as much as possible an intensive splitting and consequent formation of hydrocarbons of low molecular Weight; withdrawing the lowerboiling reaction products in a gaseous state from the reaction vessel to separate them from thehi h-boiling residue, While the reaction mass is still at high temperature; and again heatingl the high-boiling residue under pressure in t e presence of hydrogen and of an iodine-containing contact mass for converting the residue into lower-boiling hydrocarbons.

4. A process for the production of liquid hydrocarbons from carbonaceous materials, which comprises heating carbonaceous material under elevated pressure in the presence of hydrogen and ofamolybdenum-containing contact mass at elevated temperature to avoid as much as possible an intensive splitting and consequent formation of hydrocarbons of low molecular weight; withdrawing the lowerboiling reaction products in a gaseous state from the reaction vessel to separate them from the high-boiling residue, While the reaction mass is still at high temperature; again heating the high-boiling residue under pressure in the presence of hydrogen and of an iodine-containing contact mass for con-.

verting the residue into lower-boiling hydrocarbons; separating the lower-boiling reacrescues tion products obtained in the second heating treatment from the high-boiling residue by withdrawing said reaction products in a gaseous state from the reaction vessel, while the reaction mass is still at high temperature; and then heating said high-boilin residue under pressure in the presence of Eydrogen and of an iodine-containing contact mass to convert the residue into lower-boiling hydrocarbons.

In testimony whereof I have aflixed my signature.

HEIN ISRAEL WATERMAN. 

